JP6687185B2 - Flexible plastic film - Google Patents

Description

  [Cross-reference of related applications]

  This application is based on Korean Patent Application No. 10-2015-0109699 dated August 3, 2015, Korean Patent Application No. 10-2015-0160673 dated November 16, 2015, Korean Patent Application dated September 15, 2015. Claiming the benefit of priority under No. 10-2015-0130564 and Korean Patent Application No. 10-2016-0998076 dated August 1, 2016, all the contents disclosed in the document of the Korean patent application are Included as part of this specification.

  The present invention relates to flexible plastic films. More specifically, the present invention relates to a flexible plastic film which exhibits high hardness but has excellent flexibility.

  Recently, with the development of mobile devices such as smartphones and tablet PCs, thinning and slimming of display substrates have been required. Glass or tempered glass is generally used as a material having excellent mechanical properties for a display window or front plate of such a mobile device. However, the glass causes the mobile device to become heavier due to its own weight, and has a problem of being damaged by an external impact.

  Therefore, plastic resins have been studied as a material that can replace glass. Plastic resin films are lightweight yet less likely to tear and fit the trend of lighter mobile devices. In particular, in order to achieve a film having high hardness and abrasion resistance, a film in which a support substrate is coated with a hard coat layer made of a plastic resin has been proposed.

  As a method of improving the surface hardness of the hard coat layer, a method of increasing the thickness of the hard coat layer is considered. In order to secure a surface hardness that can replace glass, it is necessary to achieve a certain hard coat layer thickness. However, although the surface hardness may increase as the thickness of the hard coat layer increases, wrinkles and curls increase due to curing shrinkage of the hard coat layer, and at the same time cracks and peeling of the hard coat layer tend to occur. Not practically easy to apply.

  Korean Laid-Open Patent Publication No. 2010-0041992 discloses a plastic film composition that excludes a monomer and uses a binder resin containing a UV-curable polyurethane acrylate oligomer. However, the disclosed plastic film has a pencil hardness of about 3H and is not strong enough to replace the glass panel of the display.

  On the other hand, for aesthetic and functional reasons, a display in which a part of the display device is bent or bent so as to be flexible has recently been attracting attention, and this tendency is particularly noticeable in mobile devices such as smartphones and tablet PCs. ing. However, since glass is unsuitable for use as a cover plate for protecting such a flexible display, it is necessary to substitute it with a plastic resin or the like. However, for this reason, there is a difficulty in that it is not easy to manufacture a film having a glass-level high hardness and having sufficient flexibility.

  In order to solve the above-mentioned problems, the present invention provides a flexible plastic film having high hardness and excellent flexibility and bending stability.

In order to solve the above problems, the present invention provides
A support substrate; and a film comprising an ultraviolet-curable coating layer formed on at least one surface of the support substrate,
Has a pencil hardness of 6H or more under a load of 750g,
After leaving both sides of the film 90 degrees with respect to the bottom face at room temperature with an interval of 4 mm in the middle of the film, the film was lifted from the bottom face when it was spread on a flat bottom face. A flexible plastic film having a thickness of 0.5 mm or less is provided.

  According to the flexible plastic film of the present invention, flexibility, flexibility, high hardness, scratch resistance, and high transparency are exhibited, and there is little damage to the film even in a repeated, continuous bending or folding state for a long time, and a bendable ( It can be usefully applied to bendable, flexible, rollable, or foldable mobile devices, display devices, front plates of various instrument panels, and display units.

FIG. 3 is a schematic view illustrating a method of performing a bending stability test on a film according to an embodiment of the present invention.

  The flexible plastic film of the present invention is a film including a supporting base material; and an ultraviolet-curable coating layer formed on at least one surface of the supporting base material, and shows a pencil hardness of 6H or more under a load of 750 g. After being left at room temperature with both sides of the film folded at 90 degrees with respect to the bottom surface at an interval of 4 mm in the middle, the height of the film lifted from the bottom surface was 0. It is 5 mm or less.

  In the present invention, the terms first, second, etc. are used to describe various components, and the above terms are used only to distinguish one component from another component.

  Also, the terminology used herein is used only to describe the exemplary embodiments and is not intended to limit the invention. A singular expression includes plural expressions unless the context clearly dictates otherwise. As used herein, terms such as "comprising," "comprising," or "having" are intended to specify that there are features, steps, components, or combinations thereof implemented. It should be understood that the possibility of the presence or addition of one or more other features or steps, components, or combinations thereof is not precluded.

  The present invention may be modified in various manners and have various forms, and it will be described in detail below by exemplifying specific embodiments. However, this is not intended to limit the invention to the particular disclosed form and it should be understood to include all modifications, equivalents or alternatives falling within the spirit and scope of the invention. I won't.

  Hereinafter, the flexible plastic film of the present invention will be described in more detail.

  A flexible plastic film according to an embodiment of the present invention is a film including a supporting substrate; and an ultraviolet curable coating layer formed on at least one surface of the supporting substrate, and having a pencil hardness of 6H or more under a load of 750 g. The film is lifted from the bottom surface when left at room temperature with both sides of the film folded at 90 degrees with respect to the bottom surface at an interval of 4 mm in the middle of the film and then spread on a flat bottom surface. Is 0.5 mm or less.

  In the present invention, the term "flexible" means a state in which a cylindrical mandrel having a diameter of 4 mm has a flexibility such that a crack having a length of 3 mm or more does not occur. Therefore, the flexible plastic film of the present invention is applicable to a bendable, flexible, rollable, or foldable display cover film.

  In mobile devices such as smartphones and tablet PCs, and displays such as LCDs, a part of the display device is bent or bent to be flexible, for aesthetic and functional reasons. The trend is especially noticeable on mobile devices. However, since glass is not suitable for use as a cover plate for protecting such a flexible display, it is necessary to replace it with a plastic film containing an ultraviolet curable or thermosetting resin.

  Among the cover plates made of plastic resin, the ones that have been developed so far include a curved film that is fixed with a certain curvature and a film that is flexible enough to be bent by hand. However, the development of a film having such a flexibility that cracks do not occur even when it is repeatedly bent or folded for a long time is insufficient.

  Further, if the film is thin, it is advantageous for realizing flexibility, but it is relatively disadvantageous for surface hardness. Therefore, while having high flexibility, high hardness is provided at the same time. Providing a film is not easy.

  The present invention realizes a plastic resin film containing an ultraviolet-curable coating layer so as to satisfy such a balance of physical properties of flexibility and high hardness at the same time, and exhibits high hardness, especially in a bent or folded state for a long time. Provides a flexible plastic film which can be applied to bendable, flexible, rollable, or foldable mobile devices, display devices, etc. with almost no damage to the film.

  That is, the present invention is a film comprising a supporting base material; and an ultraviolet-curable coating layer formed on at least one surface of the supporting base material, showing a pencil hardness of 6H or more under a load of 750 g, and having an intermediate thickness of the film. After being left at room temperature with both sides of the film folded at 90 degrees with respect to the bottom surface at an interval of 4 mm, when the film is spread on a flat bottom surface, the height of the film lifted from the bottom surface is 0.5 mm or less. Shows some bending stability.

  FIG. 1 is a view schematically showing a method of measuring physical properties of bending stability of a flexible plastic film according to an embodiment of the present invention.

  Referring to FIG. 1, after the film was placed horizontally on the bottom, the space between the folding parts in the middle part of the film was 4 mm, and both sides of the film were folded at 90 degrees with respect to the bottom surface. In this state, the film is left at room temperature for a certain time, for example, about 12 to about 72 hours, and then the film is spread on a flat bottom surface so that the folded portion goes down, and after one hour, the film is lifted from the bottom surface. Stability against bending can be measured by measuring height.

  At this time, in order to maintain a constant interval between the folded portions, for example, the film is placed so as to hit a rod having a diameter (R) of 4 mm, the remaining portion of the film is fixed, and both sides of the film are folded around the rod. You can take the way. The folded portion is not particularly limited as long as it is inside the film, and for convenience of measurement, the center portion of the film can be folded so that the remaining both sides of the film except the folded portion are symmetrical. .

  In such a stability measurement, the flexible plastic film of the present invention has a height lifted from the bottom surface of about 0.5 mm or less even after being left in a folded state for about 12 to about 72 hours and then unfolded again. , Or about 0.3 mm or less, or about 0.2 mm or less, and substantially the original flat state can be restored.

  Therefore, even in actual use such as folding, winding, or bending for a long time, the film may be deformed such as cracked or lifted, or a distortion phenomenon may occur at a bent or folded portion. It has a very low fear and can be suitably applied to a cover plate of a flexible display.

  Further, the flexible plastic film of the present invention may have a pencil hardness of 6H or more, or 7H or more under a load of 750g.

  As described above, reducing the thickness of the film is advantageous for realizing flexibility, but since the surface hardness is relatively low, it has high flexibility and high hardness at the same time. Providing a film is not easy. However, the flexible plastic film of the present invention achieves flexural stability for 12 hours or more and high pencil hardness of 6H or more, or 7H or more under a load of 750 g, by balancing the two contradictory physical properties.

  That is, the present invention has a structure including a support base material and a coating layer formed on at least one surface of the support base material, and has a pencil hardness of 6H or more under a load of 750 g and a bent or folded state for a predetermined time. After satisfying the physical properties that are restored to the original flat state even after maintaining, it is practically applicable to bendable, flexible, rollable, fallable mobile devices, display devices, etc. did.

  The flexible plastic film of the present invention that simultaneously satisfies such bending stability and surface hardness is realized by optimizing a supporting base material and an ultraviolet-curable coating layer (hereinafter, "coating layer") on the supporting base material. can do.

  For example, in the flexible plastic film of the present invention, the support substrate on which the coating layer is formed has an elasticity of about 4 GPa or more when measured by ASTM D882 so as to ensure flexibility and hardness. It is an optical transparent plastic resin having a modulus and a thickness in the range of 20 to 200 μm, and it can be used without any particular limitation in the manufacturing method and material of a supporting substrate such as a stretched film or a non-stretched film.

  Among the conditions for the supporting substrate, the elastic modulus may be about 4 GPa or more, or about 5 GPa or more, or about 5.5 GPa, or about 6 GPa, and the upper limit is about 9 GPa or less, or about 8 GPa or less. , Or about 7 GPa or less. If the elastic modulus is less than 4 GPa, sufficient hardness may not be achieved, and if it exceeds 9 GPa and is too high, it may be difficult to form a flexible film.

  The thickness of the supporting substrate may be about 20 μm or more, or about 25 μm or more, or about 30 μm or more, and the upper limit thereof is about 200 μm or less, or about 150 μm or less, or about 100 μm or less, or It may be about 60 μm or less. If the thickness of the supporting substrate is less than 20 μm, it may break or curl during the coating layer forming process, and it may be difficult to achieve high hardness. On the other hand, if the thickness exceeds 200 μm, the flexibility may be reduced and it may be difficult to form a flexible film.

  Thus, in view of ensuring processability for the flexible film and balancing physical properties of high hardness and flexibility, the plastic film of the present invention has an elastic modulus of 4 GPa or more and 9 GPa or less and a thickness of Can be used in the range of 20 to 200 μm.

  More specifically, according to one embodiment of the present invention, the supporting base material satisfies the elastic modulus and the thickness range described above, and includes, for example, polyimide (PI) and polyimide amide (polyimideamide). ), Polyether imide (PEI), polyethylene terephthalate (PET), polyethylene naphthalate (polyethylene terephthalate, PEN), polyether ether ketone (polyetherether ethercene, PEEK), cyclic olefin (PEEK), cyclic olefin. , Polyacrylate (PAC), polymer It may be a film containing tylmethacrylate (PMMA), triacetylcellulose (TAC), or the like. The supporting substrate may have a single layer or a multilayer structure including two or more substrates made of the same or different substances, if necessary, and is not particularly limited.

  Alternatively, according to an embodiment of the present invention, the supporting substrate may be a substrate including polyimide (PI).

  Also, according to an embodiment of the present invention, the thickness ratio of the support substrate and the coating layer is about 1: 0.05 to about 1: 1 or about 1: 0.1 to about 1: It may be 0.8. When the thickness ratio of the supporting base material and the coating layer is within the above range, a flexible plastic film exhibiting high hardness and flexibility can be more easily formed.

  The flexible plastic film of the present invention includes an ultraviolet curable coating layer formed on at least one surface of the supporting substrate.

  According to an embodiment of the present invention, the coating layer is formed on both sides of the supporting substrate.

In the flexible plastic film of the present invention, the coating layer is a cross-linked copolymer of a 3 to 6 functional acrylate binder and a 7 to 20 functional urethane acrylate binder, and first inorganic fine particles having a d50 of ₂₀ to 35 nm. Group and the second inorganic fine particle group having d ₅₀ of 40 to 130 nm, and thus the inorganic fine particle having a bi-modal particle distribution.

  Throughout the present specification, the acrylate type means not only acrylate but also methacrylate or a derivative in which a substituent is introduced into acrylate or methacrylate.

  The 3- to 6-functional acrylate-based binder may be cross-linked with the 7- to 20-functional urethane acrylate-based binder to form a copolymer, and impart high hardness to the coating layer formed after curing.

  As a more specific example, the 3- to 6-functional acrylate-based binder is trimethylolpropane triacrylate (TMPTA), trimethylolpropane ethoxytriacrylate (TMPEOTA), glycerin propoxylated triacrylate (GPTA), pentaerythritol. Tetraacrylate (PETA), dipentaerythritol hexaacrylate (DPHA), etc. are mentioned. The 3- to 6-functional acrylate-based binders may be used alone or in combination with each other.

  According to an embodiment of the present invention, the 3- to 6-functional acrylate-based binder has a weight average molecular weight (Mw) of about 200 to about 2,000 g / mol, or about 200 to about 1,000 g / mol, or It may range from about 200 to about 500 g / mol.

  Also, according to an embodiment of the present invention, the 3- to 6-functional acrylate-based binder has an acrylate equivalent weight of about 50 to about 300 g / mol, or about 50 to about 200 g / mol, or about 50. To about 150 g / mol.

  When the weight average molecular weight and the acrylate equivalent of the 3- to 6-functional acrylate-based binder are within the ranges described above, a coating layer having more optimized physical properties can be formed.

  The 7 to 20 functional urethane acrylate binder is cross-linked with the 3 to 6 functional acrylate binder to form a copolymer, and the coating layer formed after curing has high hardness, flexibility and impact resistance. Can be given. The 7 to 20 functional urethane acrylate-based binder may be used alone or in combination of different types.

  According to one embodiment of the present invention, the cross-linked copolymer comprises about 3 to 6 functional acrylate-based binder and 7 to 20 functional urethane acrylate-based binder from about 1: 9 to about 5: 5, preferably about. It may be cross-linked and polymerized in a weight ratio of 1: 9 to about 4: 6, more preferably about 1: 9 to about 3.5: 6.5. By including a cross-linked copolymer in which a 3- to 6-functional acrylate binder and a 7- to 20-functional urethane acrylate binder are cross-linked in the above weight ratio, sufficient flexibility is exhibited, and at the same time, good physical properties of high hardness. Can be achieved.

  According to an embodiment of the present invention, the 7-20 functional urethane acrylate-based binder has a weight average molecular weight of about 2,000 to about 8,000 g / mol, or about 3,000 to about 6,000 g / mol. , Or about 3,000 to about 5,000 g / mol is preferable for optimizing the physical properties of the coating layer.

  In addition, according to an embodiment of the present invention, the 7-20 functional urethane acrylate-based binder has an acrylate equivalent weight of about 200 to about 1,500 g / mol, or about 200 to about 1,000 g / mol. It may be in the range of mol, or about 300 to about 600 g / mol, or about 300 to about 500 g / mol. If the acrylate equivalent of the 7-20-functional urethane acrylate-based binder is too high, the hardness of the coating layer may not be sufficient. If the equivalent is low, the hardness may be improved but the flexibility may be decreased. As mentioned above, from the viewpoint of the balance between high hardness and flexibility, the above-mentioned equivalent range is preferable, and about 300 to about 500 g / mol is most preferable.

  When the weight average molecular weight and the acrylate equivalent of the 7-20 functional urethane acrylate-based binder are within the ranges described above, a coating layer having more optimized physical properties can be formed.

  The 7 to 20-functional urethane acrylate-based binder contains 7 or more acrylate groups capable of being cross-linked and polymerized by ultraviolet rays in the molecule, and thus has a very high bond density and is advantageous for achieving high hardness of the coating layer. is there. However, the higher the cross-linking density, the more easily curling occurs and the adhesion to the substrate decreases, which is not suitable for forming a flexible film.

  Meanwhile, the 7 to 20 functional urethane acrylate-based binder included in the coating layer according to the exemplary embodiment of the present invention includes 7 or more polyfunctional acrylate groups, and at the same time has a urethane bond in the molecule, and has elasticity and elasticity. It has excellent flexibility. Therefore, when a copolymer is formed by being cross-linked with a 3 to 6-functional acrylate-based binder in an appropriate weight ratio, it serves to impart high hardness and sufficient flexibility to the coating layer. The 7 to 20 functional urethane acrylate-based binder may include 2 to 20 urethane bonds in one molecule.

  As described above, the coating layer according to the exemplary embodiment of the present invention includes the cross-linked copolymer in which the 3 to 6 functional acrylate-based binder and the 7 to 20 functional urethane acrylate-based binder are cross-linked to form a flexible plastic. It imparts high hardness and flexibility to the film, has high stability especially against bending, rolling or folding, and there is little risk of deformation of the film even when it is bent or folded for a long time, Very good flexibility and stability can be ensured.

Coating layer according to an embodiment of the present _invention, a bimodal (bi-modal) particle distribution by including _{d 50} of the first inorganic fine particles group and _{d 50} of 20~35nm the second inorganic fine particles group 40~130nm Including inorganic fine particles having. As described above, the coating layer according to the exemplary embodiment of the present invention is flexible by using the inorganic fine particles having a bimodal distribution by including the first and second inorganic fine particle groups having d ₅₀ in a specific range. High hardness and flexibility of the coating layer can all be achieved at the same time while maintaining the properties.

In the specification of the present invention, a laser light diffraction method (measurement method: Dynamic laser scattering, a solvent in which inorganic fine particles are dispersed, a refractive index, a viscosity, and a dielectric constant of the inorganic fine particles are used to obtain a size distribution by number, a device name: when the Malvern Zetasizer Nano-ZS90) was measured cumulative particle size distribution degree according to the particle diameter, cumulative 10% particle size of _{d 10} of 50% cumulative particle size of _{d 50,} the cumulative 90% particle size d ₉₀ . The particle size distribution by the laser light diffraction method is measured by diluting a dispersion liquid in which inorganic particles are dispersed in a solvent and measuring by SEM or TEM, or by analyzing the cross section of the coating layer containing the inorganic particles by SEM or TEM. The distribution can be substantially the same as that shown.

  The first group of inorganic fine particles having a small particle size range contributes to the improvement of hardness, and the group of second inorganic fine particles having a larger particle size range contributes to the improvement of flexibility and flexibility. By mixing and using the inorganic fine particle group having a different particle size range in addition to the copolymer, it is possible to provide a coating layer having simultaneously improved physical properties of hardness and flexibility.

  For the first and second inorganic fine particle groups, for example, silica fine particles, aluminum oxide particles, titanium oxide particles, zinc oxide particles, or the like can be used independently of each other.

According to an embodiment of the present invention, the d ₅₀ of the first group of inorganic fine particles is 20 nm or more, or about 21 nm or more, and may be 35 nm or less, 30 nm or less, or 25 nm or less. The d _{50 of the} inorganic fine particle group is 40 nm or more, or about 42 nm or more, or about 45 nm or more, and may be 130 nm or less, or 125 nm or less, or 120 nm or less.

Further, according to an embodiment of the present invention, the first inorganic fine particle group may have d _{10 of 10} to 19 nm, d ₅₀ of 20 to 35 nm, and d ₉₀ of 25 to 40 nm. Further, in the second group of inorganic fine particles, d ₁₀ may be 25 to 110 nm, d ₅₀ may be 40 to 130 nm, and d ₉₀ may be ₆₀ to 150 nm.

  According to one embodiment of the present invention, the content of the first inorganic fine particle group is about 5 parts by weight or more, or about 10 parts by weight to contribute to the improvement of high hardness, relative to 100 parts by weight of the entire coating layer. May be more than or equal to about 15 parts by weight, and about 50 parts by weight or less, or about 45 parts by weight or less, or about 40 parts by weight or less, or about 35 parts by weight or less to satisfy the flexibility. May become. By including the first inorganic fine particle group in the weight range, it is possible to form a flexible plastic film having excellent physical properties that simultaneously satisfies high hardness and flexibility.

  Further, according to one embodiment of the present invention, the content of the second inorganic fine particle group is about 5 parts by weight or more, or 100 parts by weight of the entire coating layer, in order to contribute to the improvement of high hardness, or It may be about 10 parts by weight or more, or about 15 parts by weight or more, and to satisfy the flexibility, about 50 parts by weight or less, or about 45 parts by weight or less, or about 40 parts by weight or less, or about 35 parts by weight. It may be less than a part. By including the second inorganic fine particle group in the weight range, it is possible to form a flexible plastic film having excellent physical properties that simultaneously satisfies high hardness and flexibility.

  Further, according to one embodiment of the present invention, the total content of the inorganic fine particles including the first and second inorganic fine particle groups contributes to the improvement of high hardness with respect to 100 parts by weight of the entire coating layer. , About 25 parts by weight or more, or about 30 parts by weight or more, or about 35 parts by weight or more, and to satisfy flexibility, about 50 parts by weight or less, or about 45 parts by weight or less, or about 40 parts by weight. It can be adjusted to less than or equal to parts by weight.

  According to an embodiment of the present invention, the first and second inorganic fine particle groups are independently the same or different and have a surface of (meth) acrylsilane (meth) acrylsilane and methacryloxysilane. It may be modified with any one or more silane coupling agents selected from the group consisting of vinyl silane, epoxy silane, epoxy silane, and mercapto silane.

  As described above, the first and second inorganic fine particle groups surface-modified with the silane coupling agent are capable of reacting with the acrylate group of the binder, have high adhesion to the base material, and are uniformly dispersed in the coating layer. It may be more advantageous because it is possible and the hardness can be improved without reducing the flexibility of the coating layer.

  According to an embodiment of the present invention, the first and second groups of inorganic fine particles comprise about 9: 1 to about 3: 7, or about 8: 2 to about 4: 6, or about 7: 3 to about 5. : 5 weight ratio. By including the first and second inorganic fine particle groups in the range of the weight ratio, it is possible to form a flexible plastic film having higher hardness and flexibility and excellent physical properties.

  On the other hand, the coating layer of the present invention, in addition to the binder, the inorganic fine particles, the photoinitiator, and the organic solvent described above, a surfactant, a UV absorber, a UV stabilizer, an anti-yellowing agent, a leveling agent, an antifouling agent, Additives commonly used in the technical field of the present invention, such as dyes for improving color value, may be additionally included. In addition, the content thereof is not particularly limited because it can be variously adjusted within a range that does not deteriorate the physical properties of the coating layer of the present invention, but is, for example, about 0.01 to 100 parts by weight of the coating layer. About 10 parts by weight is included.

  According to an embodiment of the present invention, for example, the coating layer may include a surfactant as an additive, and the surfactant may be a mono- or difunctional fluorine-based acrylate or a fluorine-based surfactant. It may be an agent or a silicone-based surfactant. At this time, the surfactant is included in the coating layer in a dispersed or crosslinked form.

  In addition, the additive may include a UV absorber or a UV stabilizer, and the UV absorber may include a benzophenone compound, a benzotriazole compound, a triazine compound, or the like. Examples thereof include tetramethylpiperidine and the like.

The coating layer according to the exemplary embodiment of the present invention includes a 3 to 6 functional acrylate binder, a 7 to 20 functional urethane acrylate binder, a photoinitiator, a first inorganic fine particle group having a d50 of ₂₀ to 35 nm, and The coating composition containing the inorganic fine particles having a bimodal particle distribution by including the second inorganic fine particle group having d ₅₀ of 40 to 130 nm, the additive, and the organic solvent can be photocured to be formed.

  Examples of the photoinitiator include 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl]-. 2-Methyl-1-propanone, methylbenzoyl formate, α, α-dimethoxy-α-phenylacetophenone, 2-benzoyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1- Butanone, 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide, or bis (2,4 , 6-trimethylbenzoyl) -phenylphosphine oxide and the like, but are not limited thereto. In addition, currently commercially available products include Irgacure 184, Irgacure 500, Irgacure 651, Irgacure 369, Irgacure 907, Darocur 1173, Darocur MBF, Irgacure 819, Darocur TPO, Irgacure 907, and Ergacure 907. These photoinitiators can be used alone or in admixture of two or more different from each other.

  Examples of the organic solvent include alcohol solvents such as methanol, ethanol, isopropyl alcohol and butanol, alkoxy alcohol solvents such as 2-methoxyethanol, 2-ethoxyethanol and 1-methoxy-2-propanol, acetone and methyl ethyl ketone. Ketone solvents such as methyl isobutyl ketone, methyl propyl ketone, cyclohexanone, propylene glycol monopropyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethyl glycol Monoethyl ether, diethyl glycol monopropyl ether, diethyl glycol Monobutyl ether, ether solvents such as diethylene glycol 2-ethylhexyl ether, benzene, toluene, and aromatic solvents such as xylene, can be used alone or in combination.

  The content of the organic solvent is not particularly limited, as it can be variously adjusted within a range that does not deteriorate the physical properties of the coating composition, but is not limited to the solid content in the components contained in the coating composition. The organic solvent may be included in a weight ratio of about 30:70 to about 99: 1. When the organic solvent is in the above range, it may have suitable fluidity and coatability.

  The coating composition may be sequentially applied to the front surface and the rear surface of the supporting substrate, or may be simultaneously applied to both surfaces of the supporting substrate.

  According to one embodiment of the present invention, a flexible plastic film of the present invention is prepared by applying a coating composition containing the above components on both surfaces of the supporting substrate and then photo-curing the coating composition to form a coating layer. Obtainable. At this time, the method of applying the coating composition is not particularly limited as long as it can be used in the technical field to which the present technology belongs, for example, bar coating method, knife coating method, roll coating method, blade coating method, A die coating method, a micro gravure coating method, a comma coating method, a slot die coating method, a lip coating method, a solution casting method and the like can be used.

  The coating layer may have a thickness of about 3 μm or more, for example, about 3 to about 20 μm, or about 3 to about 15 μm, or about 3 to about 10 μm after being completely cured. According to one embodiment of the present invention, a flexible plastic film having high hardness can be provided when the coating layer having such a thickness is included.

  According to an embodiment of the present invention, the flexible plastic film comprises a plastic resin film, an adhesive film, a release film, and a conductive film on the upper surface of at least one coating layer or between the base film and the coating layer. , A conductive layer, a liquid crystal layer, a coating layer, a cured resin layer, a non-conductive film, a metal mesh layer, or a patterned metal layer, a layer, a film, or the like. For example, an antistatic layer having conductivity is first formed on a supporting substrate, and then a coating layer is formed thereon to impart an antistatic function, or a low refractive index layer is formed on the coating layer. Can be introduced to realize a low reflection function.

  In addition, the layer, the film, the film, or the like may be a single layer, a double layer, or a laminated type. The layer, the film, or the film may be laminated on the coating layer by laminating a freestanding film with an adhesive or a sticky film, or by coating, vapor deposition, or sputtering. However, the present invention is not limited to this.

  The flexible plastic film according to the present invention can be manufactured, for example, by the following method.

  According to one embodiment of the present invention, first, a first coating composition is first applied and first photocured on one surface of a supporting substrate, and then the other surface of the supporting substrate, that is, a back surface is coated again with the coating composition. It can be formed by a two-step process of second coating and second photo-curing. At this time, the first and second coating compositions are the same as the above-mentioned coating compositions, and merely distinguish the compositions applied to one side and the back side, respectively.

  When the coating layer is formed by such a method, in the second photo-curing step, the UV irradiation is performed on the opposite side of the surface on which the first coating composition is applied. By offsetting possible curls in opposite directions, a flat flexible plastic film can be obtained. Therefore, no additional planarization process is necessary.

  However, the present invention is not limited thereto, and the curl balance can be adjusted by simultaneously applying the coating composition on both surfaces of the supporting substrate and then curing the coating composition.

  INDUSTRIAL APPLICABILITY The flexible plastic film of the present invention exhibits excellent flexibility, flexibility, high hardness, scratch resistance, high transparency, high durability against bending, winding or folding, stability, and the like. It is used as a cover film for a next-generation display having bendable, flexible, rollable, or foldable characteristics.

  For example, the flexible plastic film of the present invention may exhibit such flexibility that it does not crack when wound on a cylindrical mandrel having a diameter of 4 mm or 3 mm.

  Further, the flexible plastic film of the present invention may have a pencil hardness of 6H or more, or 7H or more under a load of 750g.

  Further, the flexible plastic film of the present invention was loaded on a friction tester with steel wool # 0000 on a tip having a contact area of 2 cm × 2 cm with respect to the plastic film, and then loaded with 500 g. When the surface of the plastic film is reciprocated 400 times, the number of scratches is 2 or less.

  The flexible plastic film of the present invention has a light transmittance of 88.0% or more, or 90.0% or more, and a haze of 1.5% or less, or 1.0% or less, or 0.5% or less. May be

  Such a flexible plastic film of the present invention can be used in various fields. For example, not only a flat type, but also a curved, bendable, flexible, rollable, or foldable type mobile communication terminal, a touch panel of a smartphone or a tablet PC, and various types. It can be used as a display cover substrate or element substrate.

  Hereinafter, the operation and effect of the present invention will be described in more detail through specific examples of the present invention. However, such an embodiment is presented only as an example of the invention, and does not define the scope of rights of the invention.

  <Example>

Example 1
Trifunctional acrylate binder trimethylolpropane triacrylate (TMPTA) (Manufacturer: Cytec, Mw = 296 g / mol, acrylate group equivalent = 99 g / mol) 30 g, 9-functional urethane acrylate binder MU9800 (manufacturer: MIWON, Mw = 3500 g / mol, acrylate group equivalent = 389 g / mol) 40 g, 10-functional urethane acrylate binder MU9020 (manufacturer: MIWON, Mw = 4500 g / mol, acrylate group equivalent = 450 g / mol) 30 g, light An acrylate solution was prepared by mixing 1 g of an initiator Irgacure 184 (manufacturing company: Ciba) and 15 g of methyl ethyl ketone (MEK).

In this acrylate solution, silica particles S1 (d ₁₀ = 17 nm, d ₅₀ = 22 nm, d ₉₀ = 28 nm, surface-modified with a methacrylate silane coupling agent) were added to n-BA (normal butyrate acetate) in an amount of 50% by weight. % 60% dispersion solution (hereinafter, S1 dispersion solution), silica particles S2 (d ₁₀ = 29 nm, d ₅₀ = 51 nm, d ₉₀ = 74 nm, which are surface-modified with an acrylate silane coupling agent) are MEK. A coating composition was manufactured by mixing 50 g of a solution having 30% by weight dispersed therein (hereinafter, S2 dispersion solution).

  The coating composition is applied to both sides of a polyimide substrate (size: 20 cm × 30 cm, thickness: 35 μm) having an elastic modulus value of 6.0 GPa measured by ASTM D882 by a bar coating method, and a metal halide having a wavelength of 290-320 nm. A coating layer was formed by photocuring with a lamp.

  After the curing was completed, the thickness of the coating layer formed on each side was 6 μm.

Example 2
A coating layer was formed in the same manner as in Example 1 except that the S2 dispersion solution was 83.3 g in Example 1 and did not contain a separate methyl ethyl ketone solvent.

Example 3
In Example 1, 25 g of methyl ethyl ketone was used, and instead of 50 g of the S2 dispersion solution, silica particles S3 (d ₁₀ = 108 nm, d ₅₀ = 119 nm, d ₉₀ = 131 nm, and surface modified with an acrylate silane coupling agent). Was mixed with MEK in an amount of 40% by weight (hereinafter referred to as S3 dispersion solution) to prepare a coating composition.

  In the subsequent steps, the coating layer was formed in the same manner as in Example 1.

Example 4
TMPTA (manufacturing company: Cytec, Mw = 296 g / mol, acrylate group equivalent = 99 g / mol) 20 g, MU9800 (manufacturing company: MIWON, Mw = 3500 g / mol, acrylate group equivalent = 389 g / mol) 40 g, MU9020 (manufacturing company) : MIWON, Mw = 4500 g / mol, acrylate group equivalent = 450 g / mol) 40 g, photoinitiator Irgacure 184 (manufacturer: Ciba) 1 g, and methyl ethyl ketone (MEK) 12 g were mixed to prepare an acrylate solution.

  A coating composition was manufactured by mixing 60 g of the S1 dispersion solution and 75 g of the S3 dispersion solution with the acrylate solution.

  In the subsequent steps, the coating layer was formed in the same manner as in Example 1.

Example 5
A coating layer was formed in the same manner as in Example 1 except that a polyimide substrate (size: 20 cm × 30 cm, thickness: 35 μm) having an elastic modulus value measured by ASTM D882 of 4.2 GPa was used. did.

Example 6
A coating layer is formed in the same manner as in Example 1 in the remaining steps except that a polyimide substrate (size: 20 cm × 30 cm, thickness: 35 μm) having an elastic modulus value of 7.6 GPa measured by ASTM D882 is used. did.

Example 7
TMPTA (manufacturing company: Cytec, Mw = 296 g / mol, acrylate group equivalent = 99 g / mol) 30 g, MU9020 (manufacturing company: MIWON, Mw = 4500 g / mol, acrylate group equivalent = 450 g / mol) 30 g, 15-functional urethane Acrylic binder SC2152 (manufacturer: MIWON, Mw = 20,000 g / mol, acrylate group equivalent = 1,333 g / mol) 40 g, photoinitiator Irgacure184 (manufacturer: Ciba) 1 g, and methyl ethyl ketone (MEK) 42 g are mixed. To produce an acrylate solution.

  A coating composition was prepared by mixing 60 g of the S1 dispersion solution and 83.3 g of the S2 dispersion solution with the acrylate solution.

  In the subsequent steps, the coating layer was formed in the same manner as in Example 1.

Example 8
AZO particle dispersion CX-610M (manufacturing company: Nissan, solid content 60%) 20 g, dipentaerythritol pentaacrylate (DPHA) 10 g, photoinitiator Irgacure 184 (manufacturing company: Ciba) 0.5 g, and ethanol 100 g are mixed. Thus, an antistatic layer composition was produced.

The antistatic layer composition was applied onto one surface of the polyimide substrate used in Example 1 and photocured to form an antistatic layer having a thickness of 1 μm and a surface resistance of 10 ⁹ Ω / sq.

  The coating composition of Example 1 was applied to the upper surface of the antistatic layer and the other surface of the substrate on which the antistatic layer was not formed, and photocured to form coating layers each having a thickness of 6 μm. Formed.

Example 9
First, a coating layer was formed on both surfaces of a polyimide substrate in the same process as in Example 1.

  Hollow silica dispersion Thrulya 4320 (manufacturing company: catalyst formation, solid content 20%) 22 g, dipentaerythritol pentaacrylate (DPHA) 4 g, photoinitiator Irgacure 184 (manufacturing company: Ciba) 0.5 g, fluorine-containing compound RS907 (manufacturing) Company: DIC, solid content 30%) 3 g was mixed to produce a low refractive index layer composition.

  The low refractive index layer composition was applied onto the coating layer and then photocured to form a low refractive index layer having a thickness of 120 nm and an average reflectance of 2%.

Comparative Example 1
A coating layer was formed in the same manner as in Example 1 except that 55 g of methyl ethyl ketone was used in Example 1 and the coating composition did not contain silica particles.

Comparative example 2
In Example 1, 12 g of methyl ethyl ketone was used, and 40% by weight of silica particles S4 (d ₁₀ = 12 nm, d ₅₀ = 17 nm, d ₉₀ = 21 nm and surface-modified with an acrylate silane coupling agent) were dispersed in MEK. A coating layer was formed in the same manner as in Example 1 except that 112.5 g of the solution (hereinafter, S4 dispersion solution) was used.

Comparative Example 3
A coating layer was formed in the same manner as in Example 1 except that the amount of methyl ethyl ketone was 35 g and the amount of the S1 dispersion solution was 110 g.

Comparative Example 4
A coating layer was formed in the same manner as in Example 1 except that 125 g of the S3 dispersion solution and 25 g of the S4 dispersion solution were used in Example 1 and that a separate methyl ethyl ketone solvent was not included.

Comparative Example 5
A coating layer was formed in the same manner as in Example 1 in the remaining steps, except that a polyimide base material (size: 20 cm × 30 cm, thickness: 35 μm) having an elastic modulus value of 3.1 GPa measured by ASTM D882 was used. did.

Comparative Example 6
A coating layer was formed in the same manner as in Example 1 except that a polyethylene terephthalate base material (size: 20 cm × 30 cm, thickness: 250 μm) having an elastic modulus value of 4.2 GPa measured by ASTM D882 was used. Formed.

Comparative Example 7
In Comparative Example 3, 70 g of PS 610 (manufacturer: MIWON, Mw = 5,400 g / mol, acrylate group equivalent = 900 g / mol), which is a hexafunctional polyester acrylate binder, was used without using MU9800 and MU9020. For example, a coating layer was formed in the same manner as in Comparative Example 3 in the remaining steps.

  The main components of the coating layers of Examples 1 to 7 and Comparative Examples 1 to 7 are summarized in Tables 1 and 2 below.

In Examples and Comparative Examples, the particle size distribution (d ₁₀ , d ₅₀ , d ₉₀ ) of the inorganic fine particles was measured in a dispersed solution state using a Malvern Zetasizer Nano-ZS90, and a distribution according to the particle size (size distribution by). number).

  * In Tables 1 and 2, the content of the inorganic fine particles is represented by a net weight of only the inorganic fine particles (S1 to S4) excluding the solvent according to the weight% of the inorganic fine particles dispersed in the solvent.

  <Experimental example>

  <Measurement method>

1) Pencil hardness Using a pencil hardness tester, the maximum hardness without scratches was confirmed after reciprocating 3 times at a load of 750 g and an angle of 45 degrees according to measurement standard JIS K5400-5-4.

2) Transmittance and haze The transmittance and haze were measured using a spectrophotometer (device name: COH-400).

3) Bending test Each film was sandwiched between cylindrical mandrels of various diameters by the method of measurement standard JIS K5600-5-1 and wound, and then the minimum diameter of 3 mm or longer in which cracks did not occur was measured.

4) Bending Stability Test FIG. 1 is a diagram schematically showing a method of performing a bending stability test on a film according to an embodiment of the present invention.

  Similar to the bending durability test, the films of Examples and Comparative Examples were cut, but laser cut to a size of 80 × 140 mm so as to minimize fine cracks at edge portions.

  The laser-cut film was placed on the fixing device and fixed so that the distance between the folded portions was 4 mm. After leaving both sides of the film at 90 degrees to the bottom for 24 hours at room temperature, peel off the film and flip it over so that the folded part goes down, and put the mouth-shaped SUS structure on it. The film was mounted and fixed. 3D image measurement of the shape of the film with non-contact type surface curvature measurement equipment (PLUTO681 (DUKIN: 605 nm laser is used, resolution 0.1 μm) is performed, and the maximum value of the height Z lifted from the bottom is determined as the bending stability. It was measured as a physical property.

  In addition, in order to measure the recoverability of the film, the film whose flexural stability was measured was allowed to stand at room temperature for 1 hour, and then the maximum value of the height Z that had risen again was measured to determine the change in the appearance of the folded part. Was visually observed.

  If Z is 0.1 mm or less and changes in appearance such as traces of the folded portion are insufficient, OK, Z exceeds 0.1 mm, or if many traces remain on the folded portion, it is displayed as NG. did.

The measurement results of the physical properties are shown in Tables 3 and 4 below.

  Referring to the above Tables 3 to 4, the film of the present invention showed good properties in all physical properties, and particularly excellent durability and stability in bending test including high hardness.

  On the other hand, the film of Comparative Example had a reduced pencil hardness or could not exhibit bending durability suitable for a flexible film.

Claims (15)

Supporting substrate;
And a film comprising an ultraviolet curable coating layer formed on at least one surface of the supporting substrate,
Has a pencil hardness of 6H or more under a load of 750g,
After leaving both sides of the film 90 degrees with respect to the bottom face at room temperature with an interval of 4 mm in the middle of the film, the film was lifted from the bottom face when it was spread on a flat bottom face. 0.5 mm or less,
The shape of the folded bent portion is cylindrical,
The thickness ratio of the supporting substrate and the coating layer is 1: 0.05 to about 1: Ri 1 der,
The support substrate has an elastic modulus of 4-9 GPa as measured by ASTM D882,
The UV-curable coating layer includes an acrylate-based binder and inorganic fine particles having a bi-modal particle distribution.
A flexible plastic film. The UV-curable coating layer includes a cross-linked copolymer of a 3 to 6 functional acrylate binder and a 7 to 20 functional urethane acrylate binder.
  The flexible plastic film according to claim 1. The inorganic fine particles are
  d _Fifty A first inorganic fine particle group of 20 to 35 nm and
  d _Fifty By including a second group of inorganic fine particles of 40 to 130 nm
  Having a bi-modal particle distribution,
  The flexible plastic film according to claim 1. The thickness of the supporting substrate is
20 to 200 μm,
The flexible plastic film according to any one of claims 1 to 3 . The thickness of the ultraviolet curable coating layer,
3 to 20 μm,
The flexible plastic film according to any one of claims 1 to 4 . The ultraviolet curable coating layer,
Cross-linked copolymer of 3 to 6 functional acrylate binder and 7 to 20 functional urethane acrylate binder;
And _{d 50} of containing inorganic fine particles having a bimodal (bi-modal) particle distribution by including first inorganic particulate group and d ₅₀ of the second inorganic fine particles group 40~130nm of 20～35Nm,
The flexible plastic film according to any one of claims 1 to 5 . The weight ratio of the 3 to 6 functional acrylate binder and the 7 to 20 functional urethane acrylate binder is
1: 9 to 4: 6,
The flexible plastic film according to claim 6 . With respect to 100 parts by weight of the UV-curable coating layer,
10 to 50 parts by weight of the 3- to 6-functional acrylate binder,
40 to 70 parts by weight of the 7 to 20 functional urethane acrylate binder,
5 to 50 parts by weight of the first inorganic fine particle group,
5 to 50 parts by weight of the second inorganic fine particle group,
The flexible plastic film according to claim 6 or 7 . The first inorganic fine particle group and the second inorganic fine particle group,
Each independently, the same or different,
Any one or more silanes selected from the group consisting of (meth) acrylic silane, methacryloxy silane, vinyl silane, epoxy silane, and mercapto silane. The surface is modified with a coupling agent.
The flexible plastic film according to any one of claims 6 to 8 . D ₁₀ of the first inorganic fine particle group is ₁₀ to 19 nm,
d ₉₀ is 25 to 40 nm,
D ₁₀ of the second group of inorganic fine particles is 25 to 110 nm,
d ₉₀ is 60 to 150 nm,
The flexible plastic film according to any one of claims 6 to 9 . The weight ratio of the first inorganic fine particle group and the second inorganic fine particle group is
9: 1 to 3: 7,
The flexible plastic film according to any one of claims 6 to 10 . The supporting substrate is
Polyimide (PI), Polyimideamide (Polyimideamide), Polyetherimide (Polyetherimide, PEI), Polyethylene terephthalate (Polyethylene terephthalate, PET), Polyethylene naphthalate, Polyetherene ethereal ether, Polyetherene ethereal ether, Polyetherene ethereate, Pene, Polyetherene ethereal ether, PEN Click olefin polymer (COP), polyacrylate (PAC), polymethylmethacrylate (PMMA), and triacetyl cellulose (triacet). Lcellulose, at least one selected from the group consisting of TAC),
The flexible plastic film according to any one of claims 1 to 11 . Further comprising an antistatic layer or a low refractive index layer on the upper or lower surface of the ultraviolet curable coating layer,
The flexible plastic film according to any one of claims 1 to 12 . When wound on a mandrel with a diameter of 4 mm,
No cracks occur,
The flexible plastic film according to any one of claims 1 to 13 .   The flexible plastic film according to claim 1, wherein the flexible plastic film has a light transmittance of 88.0% or more and a haze of 1.5% or less.